Basic Information in Capturing CO2

[1] The kinetics of CO2 reacting monoethanolamine (MEA) and 3-(methylamino)propylamine (MAPA) solutions are studied by conducting absorption rate experiments in two different apparatuses: a wetted wall column and a string of discs column. It is shown that the apparatuses give comparable results. The results are modeled using the direct kinetic mechanism with activity-based rate expressions, and good representation is obtained. [2] An absorbent structure for CO2 capture includes a honeycomb substrate having a plurality of partition walls extending in an axial direction from an inlet end to an outlet end thereby forming a plurality of flow channels. The honeycomb substrate comprises a powder component and a binder that are solidified. The absorbent structure also includes a functional mer group dispersed throughout the powder component of the partition walls of the honeycomb substrate. The functional mer group is positioned in and on the partition walls such that, when a gas stream containing CO2 flows in the flow channels from the inlet end to the outlet end, the functional mer group absorbs the CO2 by forming a coordinated bond that forms carbonate, bicarbonate, carbamates, or another coordinated or ionic compound with the CO2. [3] Ab initio calculations and a continuum model have been used to study the mechanism for formation of carbamate from CO2 and alkanolamines. The molecules studied are ethanolamine and diethanolamine. A brief review is also made of published experimental observations relevant to the reaction mechanism. The ab inito results suggest that a single-step, third-order reaction is the most likely. It would seem unlikely that a zwitterion intermediate with a significant lifetime is present in the system. A single-step mechanism also seems to be in good agreement with the experimental data. [4] Following the work of Austgen et al., the electrolyte nonrandom-two-liquid (NRTL) model was applied in a thermodynamically consistent manner to represent the vaporliquid equilibrium (VLE) of the aqueous monoethanolamine (MEA)CO2 system with rigorous chemical equilibrium consideration. Special attention was given to the accurate VLE description of the system at both absorbing and stripping conditions relevant to most aqueous MEA absorption/stripping processes for CO2 removal. The influence from chemical equilibrium constants, Henry's constant, experimental data, and data regression on the representation of the VLE of the system was discussed in detail. The equilibrium constant of the carbamate reversion reaction as well as important interaction parameters of the electrolyte NRTL model were carefully fitted to experimental data. A good agreement between the calculated values and the experimental data was achieved. Moreover, the model with newly fitted parameters was successfully applied to simulate three industrial cases for CO2 removal using a rate-based approach. The results from this work were compared with those using the model by Austgen et al. [5] The solubility and absorption rate of carbon dioxide into monoethanolamine/piperazine/water were measured in a wetted wall column at 4060C. The total amine concentration was varied from 1.0 M to 5.0 M, with monoethanolamine blends containing 0 to 1.2 M piperazine. CO2 solubility and solution speciation were simulated by nine equilibrium reactions. Two of the equilibrium constants were adjusted to match literature data. The rate of absorption was predicted by the theory of diffusion with fast chemical reaction. Piperazine at 24 mol% of the total amine decreases CO2 equilibrium pressure by 50% and

enhances the CO2 absorption rate by 50% to 100%. The CO2 enhancement factor decreases by a factor of 0.6 to 2 as loading decreases from 0 to 0.5 mol CO2/mole amine.

[6] In this chapter, firstly, CO2 capture processes based on monoenthomal (MEA) have been analyzed from the microscopic angle. Secondly, the integrations of CO2 capture processes (based on MEA) with power plants have been discussed. The main research findings are as follows: The MEA based CO2 capture process has been shown in Fig.1. The performance of the MEA based CO2 capture process has direct connection with stripper pressure, MEA inlet flowrate and weight percentage, distillate rate and reflux ratio. Based on the specific consumption analysis, the energy consumption is 4.25MJ/kgCO2, and the stripper accounts for the most energy loss. Measures can be taken to lower the energy consumption. The integration of a 600 MW supercritical power plant with a MEA based CO2 capture process has been discussed. When the system is configured so that more steam is extracted from the low turbine, modeling shows that this system has the highest thermal efficiency, about 41.92% reducing 3.22 % compared with the thermal efficiency of the original power plant.

[7] S-doped microporous carbon materials were synthesized by the chemical activation of a reducedgraphene-oxide/poly-thiophene material. The material displayed a large CO2 adsorption capacity of 4.5 mmol g-1 at 298K and 1 atm, as well as an impressive CO2 adsorption selectivity over N2, CH4 and H2. The material was shown to exhibit a stable recycling adsorption capacity of 4.0 mmol g-1. The synthesized material showed a maximum specific surface area of 1567 m2 g-1 and an optimal CO2 adsorption pore size of 0.6 nm. The microporosity, surface area and oxidized S content of the material were found to be the determining factors for CO2 adsorption. These properties show that the as synthesized S-doped microporous carbon material can be more effective than similarly prepared N-doped microporous carbons in CO2 capture. [8] A thermodynamically consistent model was developed for representing vapor-liquid equilibria in the acid gas (H2S, COJ-alkanolamine-water system. The model accounts for chemical equilibria in a rigorous manner. Activity coefficients are represented, with the Electrolyte-NRTL equation treating both longrange ion-ion interactions and local interactions between all true liquid-phase species. Both water and alkanolamine are treated as solvents. Adjustable parameters of the Electrolyte-NRTL equation, representing short-range binary interactions, were fitted on binary and ternary system VLE data. Calculated H2S and C02 equilibria are in good agreement with most of the reported experimental data for aqueous solutions of a single acid gas in monoethanolamine (MEA) and diethanolamine (DEA) in the temperature range 25-120 "C. Without fitting additional parameters, representation of experimental equilibria for mixtures of H2S and C02 in aqueous solutions of MEA or DEA is good. [9] CO2 (Carbon dioxide) emissions are one of the greenhouse gases that cause global warming. The power generation industry is one of the main emitters of CO2, and the emissions are expected to increase in the coming years as there seems to be no abatement in the consumption of fossil fuels for the production of electricity. Thus, there is a need for CO2 adsorption technologies to mitigate the emissions. However, there are several disadvantages associated with the current adsorption technologies. One of the issues is corrosion and the need for specialized equipment. Therefore, alternative and more sustainable

materials are sought after to improve the viability of the adsorption technology. In this study, several types of agricultural wastes were used as activated carbon precursors for CO2 adsorption process in a TGA (thermogravimetric analyser). The adsorption was also modelled through a pseudo-first order and second order model, Elovich's kinetic model, and an intra-particle diffusion model. From the correlation coefficient, it was found that pseudo-second order model was well-fitted with the kinetic data. In addition, activation energy below than 42 kJ/mol confirmed that the physisorption process occurred. [10] ASPEN Plus Simulation of CO2 Recovery Process Overall Process Description The process is designed to capture CO2 from flue gas and to recover food grade carbon dioxide. The process has been broken down into three separate sections: a flue gas scrubbing section, a CO2 recovery section, and a CO2 purification and liquefaction section.

The feed stream to the overall process is a portion of the flue gas from a coal-fired boiler. The main impurities to be removed for production of food grade carbon dioxide are sulfur dioxide, halides, oxides of nitrogen, and particulates, including any trace elements. Carbon dioxide further must be separated from other noncondensible gases (nitrogen, argon, oxygen, carbon monoxide), from moisture, and from any hydrocarbons, prior to storage and shipping. The process for recovery of carbon dioxide from flue gases employs monoethanolamine (MEA) as the solvent. Other acid gases present in the flue gases (SO2, SO3, HCI, HF, NO and NO2), and fly ash (particulates) result in high amine losses (predominantly through the formation of aqueous acids that react with MEA to form amine salts that cannot be regenerated through the steam stripping process). It is preferable to remove these from the gas stream prior to the carbon dioxide recovery step. This is performed in the flue gas scrubbing section. [11] In this work, plantwide control of an absorption/stripping CO2 capture process using monoethanolamine was investigated using dynamic simulation. In this system, CO2 removal ratio is influenced by operating variables such as lean solvent rate and lean solvent loading, which is in-turn determined by reboiler duty in the stripper. Moreover, we found that the long-term stability of the system cannot be achieved unless the water balance is properly maintained. Hence the following control structure was proposed. In this scheme, the CO2 removal target is guaranteed using the lean solvent feed rate to the top of the absorber column. The overall water inventory was maintained by controlling the liquid level in the reboiler of the stripping column using makeup water. In order to operate the process with an appropriate lean solvent loading, the temperature at the bottom of stripper is controlled by the reboiler duty. This control structure was tested by disturbances involving inlet flue gas flow, CO2 concentrations, and H2O concentrations as well as changes in removal targets. Dynamic simulations showed that the system can achieve removal targets and stabilize quickly while keeping optimum lean loading constant. To ensure minimum energy consumption, optimizing control can be carried out by adjusting the set point of the reboiler temperature. [12] The commercial deployment of cost-effective carbon capture technology is hindered partially by the lack of a proper suite of materials-related measurements, standards, and data, which would provide

critical information for the systematic design, evaluation, and performance of CO2 separation materials. Based on a literature search and conversations with the carbon capture community, we review the current status of measurements, standards, and data for the three major carbon capture materials in use today: solvents, solid sorbents, and membranes. We highlight current measurement, standards and data activities aimed to advance the development and use of carbon capture materials and major research needs that are critical to meet if innovation in carbon capture materials is to be achieved. The review reveals that although adsorbents are considered to have great potential to reduce carbon capture cost, there is no consensus on the experimental parameters to be used for evaluating sorbent properties. Another important finding is the lack of in-situ experimental tools for the structural characterization of solid porous materials during CO2 adsorption, and computational methods that would enable a materials-by-design approach for their development. [13] Spray towers are an effective means of capturing condensable or absorbable gases and vapors, and have long been used in a variety of applications. However, the use of a spray towers in CO 2 capture is a recent development, and the limited number of studies to date have reported experimental data only on the capture efficiency for systems with a fixed size, flow rate, and CO2 concentration of the gas mixture, as well as a fixed flow rate and absorbent concentration of the liquid mixture. Systematic investigations of the parameter space have not been reported. In this study, the capture of CO2 from a CO2/air mixture using aqueous ammonia as the absorbent medium with a single nozzle was experimentally measured over a wide range of operating conditions. Relationships between the capture efficiency and the operating parameters are reported for the first time. We also report the experimental observation of the optimum tower diameter for a given spray nozzle. [14] Membrane stripping is a promising method for carbon dioxide (CO2) desorption with low energy demand. We developed a mathematical model to simulate the CO2 stripping from the CO2-rich monoethanolamine (MEA) solvent in a hollow fibre membrane contactor. The modeling results agreed well with literature experimental results. To improve the understanding and facilitate the optimisation of the membrane based CO2 stripping process, we investigated the effects of different operating variables including liquid flow velocity, sweeping gas flow rate, regeneration pressure and temperature on CO 2 desorption performance. The effects of membranes length and diameter of membrane fi bre on CO2 desorption were also studied. Results showed that increasing membranes length will improve CO 2 stripping performance, but not infinitely due to the thermodynamic limitation of absorbent, and shorter membrane module is preferred for thinner membrane. Membranes with a smaller diameter are in favor of CO2 desorption. To predict the influence of membrane wetting on CO2 stripping performance, the change of CO2 lean loading with the wetting ratio was investigated. Membrane wetting significantly deteriorates CO2 membrane desorption performance, with CO2 lean loading increasing suddenly once the membrane is wetted. [15] Carbon dioxide adsorbents, constituted by organofunctionalized magnesium phyllosilicates, were produced using 3-aminopropyltriethoxysilane (AMPTS), N-[3-(trimethoxysilyl)propyl]-ethylenediamine (TMSPEDA), N-[3-(trimethoxysilyl)propyl]-diethylenetriamine (TMSPETA) and tetraethoxyorthosilane (TEOS) as silicon sources with N/Si ratios of 1, 0.75, 0.5 and 0.25, by conventional and microwave heating. Adsorption studies were performed using TGA and temperature programmed desorption (TPD) methods. The results showed that the best temperatures for adsorption were 41, 45 and 90 C, when magnesium phyllosilicate functionalized with TMSPETA, TMSPEDA and AMPTS respectively, were

used as adsorbents. Using TPD technique, the maximum efficiency was found to be between 0.285 and 0.899 for 100% AMPTS and 33.33% TMSPETA, obtained by conventional heating. Adsorption efficiency of the materials prepared by conventional is higher than the ones obtained using microwave as heating source, except for 100% AMPTS. Desorption kinetics of CO2, described using Avramis model, show that the CO2 desorption rate constant is in the range from 0.130 to 0.178 min-1, similar to the values for CO2 desorption from monoetamolamine-functionalized TiO2 and Li4SiO4 but in a narrower range of values. [16] The effect of synthetic routes in improving the CO2 capacity of hydrotalcite based sorbents in the temperature range 300-400 C has been studied. Ultrasonication and microwave irradiation of the synthesis gel during hydrotalcite precipitation leads to disruption in the layer stacking which in turn increases surface area. A correlation was observed between the increased surface area and improved equilibrium and dynamic CO2 capacity. A temperature dependent promotional effect of K2CO3 on CO2 capacity improvement was also observed. The CO2 loaded hydrotalcites were found to be regenerable by inert purge with or without evacuation at a slightly elevated temperature of 450 C. The dynamic CO2 capacity was found to remain stable under cyclic adsorption regeneration conditions. [17] Amine-based CO2 capture processes appear to be the near-term technology for post-combustion CO2 removal from fossil fuel power plants. However, there is no experience with large-scale application of CO2 capture on power plants. A good absorber design is necessary to handle the large volumes of dilute flue gas with high performance, low cost and energy requirement of the plant. In the present work, multiscale simulations of the absorber were investigated using Aspen RateSep, and a cost estimation model was developed based on mass and energy balances produced by the Aspen Plus simulations, and data from Turton et al. (2012) were applied for cost estimation. Investment costs (CAPEX) and energy requirements of the lean amine circulation pump and absorber blower for variations in the absorber design were compared for two cases: CO2 absorption from a coal-fired power plant, and CO2 absorption from a gas-fired power plant both with a net power output of 400 MWe. The flue gas flow rate in the gas-fired power plant case is higher than for the coal-fired power plant, over the same net power output. In the gasfired power plant case the absorber needs to be designed to process high volumes of flue gas and the pressure drop will often be higher than for a coal-fired power plant due to higher gas velocity. This results in higher capital and operating costs. Possible re-design of the absorber is studied and the results show that large electrical energy savings in the feed gas blower can be obtained when a design is chosen giving reduced absorber pressure drop. This can be achieved if the column cross sectional area is increased. This is offset by extra capital cost by a need for slightly more volume of packing. The operational design flexibility in a CO2 capture plant for a gas-fired power plant is higher than for a coal-fired power plant. [18] The chemical capture of CO2 by either aqueous Na2CO3 and K2CO3 or nonaqueous solutions of the amines 2-amino-2-methyl-1-propanol (AMP) or piperazine (PZ) is described. The captured CO2 is stored as solid NaHCO3, KHCO3, and AMP or PZ carbamates. Solid NaHCO3 and KHCO3 are decomposed at 200 C and 250 C, respectively, to regenerate the carbonates for their reuse. In the experiments with AMP or PZ, the solid carbamates are decomposed at 80 C110 C to regenerate the free amines. The absence of water in the desorption-regeneration step is intriguing and could have the potential of reducing one of the major disadvantages of aqueous absorbents, namely the energy cost of the regeneration step and amine degradation, yet preserving the efficiency of the absorption in the liquid phase.

[19] The effects of flue gas composition on carbon steel (1020) corrosion in the MEA-based CO2 capture process was studied by varying impurities which represented different levels of components in the flue gas stream over a base-case condition of just an aqueous MEA, CO2 and O2. The components studied were NaCl, HCl, FeCl2, Na2SO4, FeSO47H2O, H2SO4 (from fly ash), HNO3 (from NO2); and H2SO4 and H2SO3 (from SO3 and SO2, respectively). The results illustrated that NaCl, HCl, Na2SO4, FeSO47H2O, H2SO4, and HNO3 all accelerated the corrosion process; while, FeCl2 slowed down rate of carbon steel corrosion. Surprisingly, H2SO3, NaHSO3, and Na2SO3, either behaved as corrosion promoters, or corrosion inhibitors; depending strongly on their concentrations. [20] Absorption heat transformer (AHT) and flash evaporator (FE) are used to reduce the heat consumption of CO2 capture processes and an AHT-FE-aided capture system is proposed. Analyses are carried out to verify the effectiveness in reducing heat consumption. Compared with the base CO2 capture system of 3000t/d CO2 capture capacity from a 660MW coal-fired power unit, the AHT-FE-aided capture system reduces the heat consumption from 3.873GJ/tCO2 to 3.772GJ/tCO2, and the corresponding energy saving is 2.62%. The economic analysis shows that the annual profit would be 2.94 million RMB Yuan. The payback period of the AHT-FE-aided capture system is approximately 2.4 years. Therefore, the AHT-FE-aided capture system is both economically and technically feasible for improving the CO 2 capture energy performance. [21] In the context of CO2 emissions reduction from power plants, CO2 removal from flue gas by chemical absorption with monoethanolamine is analyzed in detail. By applying process integration and multi-objective optimization techniques the influence of the operating conditions on the thermo-economic performance and on the optimal thermal integration within a power plant is studied. With the aim of performing optimization of complex integrated energy systems, simpler parameterized models of the CO 2 capture process are developed. These models predict the optimized thermo-economic performances with regard to the capture rate, flue gas flowrate and CO2 concentration. When applied to overall process optimization, the optimization time is considerably reduced without penalizing the overall power plant model quality. This approach is promising for the preliminary design and evaluation of process options including a CO2 capture unit. [22]Modeling of the dynamic behavior of post-combustion CO2 capture process and subsequent integration with power cycles and industrial processes is a topic which currently is gaining increasing interest. The transient behavior of the CO2 absorber and the solvent regenerator with respect to liquid to gas flow rates, capture rates and heat requirements need to be controlled while, at the same time, the operation of the capture unit must comply with the operation and control of the power plant. Also, the importance of control strategies for dynamic operation increases in base load thermal power plants when the requirements for load flexibility increase, e.g. as a result of more wind power and other intermittent power sources in the energy system. Furthermore, the capture cycle may also be used to reduce the load variation of the power plant by storing CO2 rich solvent during peak demand, which then may be regenerated during periods of low demand [1]. Numerous steady-state analyses of the post-combustion capture process with MEA have been published (see e.g. Wang et al. [2] and the references therein), however less work has been carried out focusing on the dynamic behavior of the process. Kvamsdal et al. [3] presented a study of transient behavior of the absorption column in the capture system with respect to capture efficiency, liquid-to-gas (L/G) ratio and solvent loading during start-up and load reduction. The study includes cases with no process control as well as capture efficiency control. Lawal et al. [4] applied

a rate-based dynamic model of the complete capture process. Different cases of process disturbances were investigated, such as reduced reboiler duty and increased flue gas flow to the system, and the effects on the capture efficiency, solvent loading and heat requirement of the process were studied. The previous work mostly focuses on the transients observed in the capture system while the interactions and consequences for the connected processes, the power plant/industrial process and the CO 2 transportation network respectively, are rarely discussed. This work includes the capture process and the connection to a power plant process with the aim to evaluate the transient behavior of the capture system with respect to typical load-change ramp rates in modern coal power plants as well as to discuss the consequences for the steam cycle and the CO2 transportation network connected to the capture system. [23]A series of multifunctional protic ionic liquids (PILs), some of which are based on a combination of primary and tertiary amines in the same moiety coupled with a carboxylic acid, have been synthesised and employed for CO2 capture, yielding absorption capacities comparable to standard absorbents. In contrast to traditional amine absorbers, CO2 was found to desorb at lower temperatures and hence could result in a significant reduction in both the energy required to strip the absorber of CO2 and the thermally activated degradation mechanisms, which in traditional absorbers result in the loss of absorber and the production of toxic compounds. The lower basicity of the amine sites resultant from PIL formation decreases the binding energy of the CO2 to the absorber. The weaker basicity is also evidenced by lower pH of the PIL CO2 absorbers, which reduces common corrosion problems associated with traditional amine absorbers. [24] Several amine-functionalized cation ILs were successfully synthesized, characterized and tested for CO2 absorption studies. Non-functionalized ILs were studied for comparison purpose. The primary amine-ILs have shown higher CO2 solubilities both on molar basis (mol of CO2/mol of IL) and on volume basis (g of CO2/L of IL), compared to non-functionalized and tertiary-amine ILs. Besides aminefunctionalization of the cation, anion of the IL has strong influence on CO2 solubility due to its contribution by physical absorption. As a result, the [TF2N]-anion amine-ILs have higher CO2 solubility than [BF4]-anion amine-ILs. Among non-amine functionalized ILs, [P(14)666][TF2N] has the highest CO2 solubility. [25] The molar heat capacities, CP, of two new potential polyamine CO2 absorbents: diethylenetriamine (DETA) and 3-(methylamino)propylamine (MAPA), their aqueous binaries, and aqueous ternaries containing piperazine (PZ) were measured at temperatures from 303.15 K to 353.15 K. Measurements were performed at atmospheric pressure by heat flow differential scanning calorimetry. A linear relation suitably represented the temperature dependence of the CP of pure amines. The excess molar heat capacities, View the MathML source, of the binary solutions were investigated, and the data were represented as function of temperature and composition using a RedlichKister-type equation. The CP of the ternary mixtures was correlated with temperature and amine concentration using the Sohnel and Novotny equation. Results showed that the calculated data agree very well with the experimental CP values at average absolute deviation values of 0.13%, 0.20, and 0.06 for the pure, binary, and ternary systems, respectively. [26] An economical and practical way of designing the optimal condition for CO2 capture processes is proposed. This learning strategy, called reinforcement learning based iterative design, is developed to learn the optimal condition from hybrid information. One is from simulation data, the other, from real plant data. The simulation data is easily accessible, but the optimal condition is restricted to a simulated

model being selected. To make up the mismatch, new info from the real process is explored. Only fewer operating data supplemented from the real process is used to update the learning scheme, so time, costs, and efforts can be saved. The fused info from the two kinds of data is also proposed. To demonstrate the effectiveness of the proposed method, design of a pilot-scale CO2 absorption-stripping experiment is conducted for recovery of CO2 from flue gases. [27] Comparison of different CO2 absorption liquids in a highly sophisticated test facility [28] Granular activated carbons (>0.5 mm) have been prepared by KOH activation at 800 C of cokes, size fraction of 0.631.25 mm, from high volatile bituminous coals. The most suitable coal is distinctive by the volatile matter content of about 33 wt.% and negative dilatation in the AudibertArnu test. The highest mechanical strength of granules is found for the activated carbons from cokes produced at 800 850 C. They are microporous materials with porous texture parameters decreasing as the KOH/coke ratio varies from 4:1 to 2:1 in the range: surface area SBET 18001200 m2 g1, micropore volume VDR 0.71 0.48 cm3 g1 and mean micropore size L0 1.120.76 nm. The granular activated carbons represent interesting properties for gas adsorption application. CO2 uptake measured at 273 K amounts to 140 cm3 g1 under atmospheric pressure and 370 cm3 g1 under 3.5 MPa, corresponding to 6.2 and 15.7 mmol g1, respectively. [29] Chemical absorption is widely regarded as the most promising technology for CO 2 capture from large industrial-sources in the short-term. The cost of CO2 capture from post-combustion power plants using MEA, the benchmark for chemical absorption, is currently over US$ 70 per tonne of CO 2 avoided. This high cost is considered as the major obstacle to current large-scale implementation of Carbon Capture and Storage (CCS). Thus, there has been significant focus on the development of new solvents with the aim to reduce costs. This study provides insights into the impact of solvent properties on the cost of capture to assist in the development of new solvents based on a 500 MW super-critical black coal power plant as the emission source. The effect of solvent properties, specifically solvent loading, heat of reaction, solvent loss and solvent concentration is examined. The effect of improvements in process design, specifically high pressure-stripper operation, advanced structured packing, use of concrete for the process vessels, and advanced heat exchangers is also evaluated. Sensitivity analysis and Monte Carlo simulation are performed to provide an estimate of the capture cost variability. The results show that the development of aqueous chemical absorption technology for CO2 capture should focus on new solvents with good stability towards SOx and NOx, high solvent concentration (above 50 %-wt.), and high working capacity (above 0.35 mole of CO2/mole of solvent). These three parameters have the most significant impact on the capture cost. Based on Monte Carlo simulation, within a 95 % confidence level, the capture cost with improved solvent properties and process design is estimated at US$ 62 - 80 per tonne of CO2, with the most likely cost of US$ 71 per tonne of CO2 avoided. This number reduces to US$ 44 59 per tonne of CO2, with the most likely cost of US$ 52 per tonne of CO2 avoided, if the Flue Gas Desulphurisation (FGD) and Selective Catalytic Reduction (SCR) units can be eliminated. KEYWORDS: CO2 capture, CCS, Chemical Absorption, Economics, Process Design, Solvent Properties [30] High energy required for the regeneration of aqueous amine solution is a great challenge for conventional CO2 capture technology to be deployed on large scale. Finding novel adsorbent with low regeneration energy and cost-effectiveness for CO2 capture is an impetus for researchers. In this study, precipitated silica (PS) was synthesized and impregnated with various amines including 2-

aminomethylpropanol (AMP), monoethanolamine (MEA), diethanolamine (DEA) and polyethyleneimine (PEI) to produce solid adsorbents. The CO2 adsorption capacity, heat capacity, and adsorption heat of adsorbents were determined. The results were used to calculate the regeneration heat of CO2 adsorption process, which then was compared with the conventional aqueous MEA 30 wt% based process. The results indicated that MEA impregnated PS (60 wt%) has the highest CO2 adsorption capacity; up to 5.3 mmole/g and PEI impregnated PS (50 wt%) has the lowest adsorption capacity among prepared solid adsorbents; 2.9 mmole/g, which is, however, higher than that of aqueous MEA 30 wt% (2.7 mmole/g). The regeneration heat required for the solid adsorbents substantially decreased in comparison with aqueous MEA 30 wt%. Regeneration heat required for PEI impregnated PS (50 wt%) was 2080 kJ/kg of CO2 that is 46.7% lower than that of aqueous MEA 30 wt%. The obtained results demonstrated that the impregnation of amine onto PS is a viable method to reduce the regeneration energy of CO2 capture process. [31] A method based on the absolute-rate theory has been used and tested for estimation of the dynamic viscosity of CO2 loaded aqueous solutions of a representative amine-monoethanolamine (MEA). In this approach the electrolyte-NRTL model is applied to estimate the activation free energy of the solution and consequently enable prediction of the dynamic viscosity of the strong electrolyte CO2: MEA: H2O system. Three different concentrations of the aqueous MEA solutions with 20, 30, and 43 wt%, at the temperature ranges from 40 to 70oC, and the CO2 loadings from 0.1 to 0.5 mole CO2 per mole amine were selected for model investigation. The model displays good prediction ability from experimental viscosity data in the whole range of system variables. It is shown that the activation free energy for the flow process can be closely estimated through the Gibbs free energy of mixing with a correction on the sign of the energy term in the model equation from positive to negative. The result reveals that, having a reliable thermodynamic model for a selected solution, the absolute-rate theory approach is applicable for estimation of the viscosity of the strong electrolyte systems such as CO2 loaded alkanolamine solutions at different, solution concentrations, temperatures, CO2 loadings, and operating pressures for various amines and amine blends. [32] In this study, a non-aqueous absorbent, 40.8 wt % piperazine (PZ)/59.2 wt% diethylene glycol (DEG), was proposed to capture CO2 in a rotating packed bed (RPB). It was observed that the 40.8 wt% PZ could dissolve into DEG without precipitation at 20 C and regeneration energy could be reduced because the heat capacity of DEG is lower than that of water. Although the viscosity of 40.8 wt % PZ/59.2 wt % DEG was 7 times as much as that of 40.8 wt % PZ/59.2 wt % H2O, the difference in CO2 capture efficiency between these two absorbents in RPB was only 7.95 % under the operation condition to satisfy 90 % CO2 capture efficiency. At the rotating speed of 1600 rpm, the heights of transfer unit of the proposed non-aqueous absorbent were all less than 6 cm, indicating the potential of volume reduction of RPB with respect to the conventional packed column even for high viscosity absorbent. The results obtained from 23 factorial design showed that the most significant operational variable of CO 2 capture efficiency for 40.8 wt% PZ/59.2 wt % DEG in RPB was gas flow rate, followed by liquid flow rate and temperature. Finally, the most appropriate operation conditions to achieve CO2 capture efficiency exceeding 90 % were found out by path of the steepest ascent. [33] Electrochemically mediated amine regeneration is a new post-combustion capture technology with the potential to exploit the excellent removal efficiencies of thermal amine scrubbers while reducing parasitic energy losses and capital costs. The improvements result from the use of an electrochemical

stripping cycle, in lieu of the traditional thermal swing, to facilitate CO2 desorption and amine regeneration; metal cations generated at an anode react with the amines, displacing the CO2, which is then flashed off, and the amines are regenerated by subsequent reduction of the metal cations in a cathode cell. The advantages of such a process include higher CO2 desorption pressures, smaller absorbers, and lower energy demands. Several example chemistries using different polyamines and copper are presented. Experimental results indicate an open-circuit efficiency of 54 % (15 kJ per mole CO2) is achievable at the tested conditions and models predict that 69 % efficiency is possible at higher temperatures and pressures. A bench scale system produced 1.6 mL min1 CO2 while operating at 0.4 volts and 42 % Faradaic efficiency; this corresponds to a work of less than 100 kJ per mole. [34] The present invention provides a resin-wafer electrodeionization (RW-EDI) apparatus including cathode and anode electrodes separated by a plurality of porous solid ion exchange resin wafers, which when in use are filled with an aqueous fluid. The apparatus includes one or more wafers comprising a basic ion exchange medium, and preferably includes one or more wafers comprising an acidic ion exchange medium. The wafers are separated from one another by ion exchange membranes. The fluid within the acidic and/or basic ion exchange wafers preferably includes, or is in contact with, a carbonic anhydrase (CA) enzyme to facilitate conversion of bicarbonate ion to carbon dioxide within the acidic medium. A pH suitable for exchange of CO2 is electrochemically maintained within the basic and acidic ion exchange wafers by applying an electric potential across the cathode and anode. [35] A series of silylated amines have been synthesized for use as reversible ionic liquids in the application of post-combustion carbon capture. We describe a molecular design process aimed at influencing industrially relevant carbon capture properties, such as viscosity, temperature of reversal, and enthalpy of regeneration, while maximizing the overall CO2-capture capacity. A strong structureproperty relationship among the silylamines is demonstrated in which minor structural modifications lead to significant changes in the bulk properties of the reversible ionic liquid formed from reaction with CO2. [36] Trace carbon dioxide (CO2) removal from an enclosed space was studied experimentally and theoretically in a hollow fibre membrane contactor using monoethanolamine (MEA) solution. Changes in trace CO2 removal performance with liquid flow rate, gas flow rate, absorption temperature and CO2 loading were investigated individually in an apparatus under well-defined and controlled experimental conditions. We developed a 2D mathematical model to predict and further analyse the experimental results. The modeling results agreed well with the experimental work. Liquid flow rate positively influences trace CO2 removal, but is not recommended for operation at a very high level. Increasing the gas flow rate improves CO2 absorption flux at the cost of reducing CO2 removal efficiency; the optimal gas flow rate for the tradeoff between CO2 removal efficiency and absorption flux is presented. The optimal absorption temperatures change with liquid CO2 loading for trace CO2 removal. CO2 removal efficiency is a decreasing function of CO2 loading; the recommended CO2 loading of MEA solution is below 0.35 mol CO2/mol MEA. To predict influences of membrane wetting on trace CO2 removal, we also propose a model that incorporates membrane wetting. The minimum breakthrough pressure are 0.38 MPa and 0.0581 MPa for fresh membrane and old membrane, respectively. Membrane wetting significantly deteriorates trace CO2 membrane absorption performance, with CO2 removal efficiency decreasing suddenly once the membrane is wetted.

[37] A rate-based model for the simulation of post-combustion CO2 capture with aqueous solutions of monoethanolamine (MEA) is presented. It is based on a recently published and carefully validated physico-chemical fluid property model. The results of the simulation are assessed using pilot plant data with four different packings on two different scales: data from a pilot plant in our own laboratory which separates approximately 10 kg CO2/h and was equipped with the sheet metal packing Sulzer Mellapak 250Y and the gauze metal packing Sulzer BX, and data from a larger pilot plant at Esbjerg, Denmark, which separates approximately 1000 kg CO2/h and was equipped with the random packing IMTP 50 and the sheet metal packing Sulzer Mellapak 2X. The reboiler duty and the rich and lean CO2-loadings are predicted within 7 % for most experiments without any adjustment of parameters to the pilot plant results. The concentration and temperature profiles are also generally well described. The modeling of the mass transfer is identified as the most important source of uncertainty of the simulation and discussed in detail. [38] An experiment system made up of a membrane absorption unit and a membrane vacuum regeneration unit was set up. Ionic liquids (ILs), 1-butyl-3-methyl-imidazolium tetrafluoroborate ([bmim][BF4]) and 1-(3-aminopropyl)-3-methyl-imidazolium tetrafluoroborate ([apmim][BF4]) as two absorbents for CO2 capture, were applied to the experiment system. Coupling processes of membrane contactor-IL absorbents and membrane vacuum-IL regenerations were evaluated by both the membrane absorption unit and the membrane vacuum regeneration unit. Water content in the ILs, CO2 loading capacity, operation conditions and modes, and regeneration factors were investigated. Results show that lower water content in [apmim][BF4] and higher water content in [bmim][BF4] were favorable for the coupling process. The aqueous [apmim][BF4] could give a high CO2 loading capacity at almost atmospheric pressure and its absorption capability was much larger than that of [bmim][BF 4] in the coupling process. CO2 partial pressure had a certain influence on the membrane fluxes of both the ILs. The liquid flowrate evidently affected the membrane flux of the coupling process with aqueous [apmim][BF4]. The aqueous [apmim][BF4] could maintain a higher initial membrane flux and give a much larger instantaneous membrane flux compared with the aqueous [bmim][BF4]. The aqueous [bmim][BF4] could be completely regenerated even at low vacuum degree, while the aqueous [apmim][BF4] was difficult to be regenerated comparatively even at high vacuum degree. [39] Adding ethanol to an aqueous amine solution offers several advantages for post-combustion CO2 capture. The equilibrium isotherms at higher temperatures shift towards lower loadings, leading to an easier desorption. At constant temperature in the desorber bottom, the desorber pressure is increased, leading to energy savings in the CO2 compression. Alternatively, at constant desorber pressure, the temperature in the desorber bottom is decreased, leading to a smaller efficiency drop of the power plant. Furthermore, the absorption rate of CO2 is enhanced by adding ethanol. In the present work, the potential of using ethanol as a co-solvent for a 0.3 g/g aqueous monoethanolamine (MEA) solution is assessed based on simulations with an equilibrium stage model. A major drawback is the volatility of ethanol. The recovery of ethanol can be achieved using a water scrubber and subsequent stripping. The recovered ethanol vapor is sent directly to the desorber for heat integration. The process with ethanol recovery results in an increased complexity of the capture plant, difficulties in controlling the water balance and higher investment costs and offers, if any, only a moderate energetic advantage. The process concept could, however, be used for other co-solvents with similar properties as ethanol but lower vapor pressures.

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